Electrochemical behavior of the Cp*(dithiolato)Co(III) complex [(η5-Cp*)Co(1,2-S2C2 B10H10-S,S′)] and its derivatives: The effect of the ligand on half-sandwich cobalt(III) complexes

Bo Young Kim; Chongmok Lee; Seung Won Chung; Young Joo Lee; Jae Youn Pak; Jaejung Ko; Sang Ook Kang

doi:10.1016/j.jorganchem.2003.09.019

Electrochemical behavior of the Cp(dithiolato)Co(III) complex [(η₅-Cp)Co(1,2-S₂C₂ B₁₀H₁₀-S,S′)] and its derivatives: The effect of the ligand on half-sandwich cobalt(III) complexes

Bo Young Kim, Chongmok Lee, Seung Won Chung, Young Joo Lee, Jae Youn Pak, Jaejung Ko, Sang Ook Kang

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

Reaction of the 16-electron dithiolatocobalt, [(η⁵- Cp*)Co(Cab^S,S′)] (1) (Cab^S,S′=1, 2-S₂C₂B₁₀H₁₀-S,S′), with a ligand L (L=CN^tBu, PMe₃, PEt₃, PHPh₂) affords the 18-electron complexes [(η⁵- Cp*)Co(Cab^S,S′)(L)] (2) in high yield. The structures of 2 in solution were probed by NMR spectroscopy, and the solid-state structure of the diphenylphosphine derivative was established by single-crystal X-ray diffraction. Cyclic voltammetry of 1 shows that the complex undergoes a quasi-reversible one-electron oxidation and reversible reduction. The voltammetry of the corresponding 18-electron complex 2 was investigated rather extensively in terms of coordination and redox chemistry, in which the influence of the enhanced steric interaction between the bulky Cp* and incoming ligand could be observed. Cyclic voltammograms of alkylidiene or acetylene adducts of dithiolatocobalt complex 1, [(η⁵-Cp*)Co{η ³-(S,S′, C′)-SC₂B₁₀ H₁₀S(C′R₂)}] [C′R₂=CHSiMe ₃ (3a), HC=CPh (3b), (COOMe)C=C(COOMe) (3c)], are also included.

Original language	English
Pages (from-to)	236-245
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	688
Issue number	1-2
DOIs	https://doi.org/10.1016/j.jorganchem.2003.09.019
State	Published - 15 Dec 2003

Bibliographical note

Funding Information:
We thank Prof. Sukbok Chang at the Korean Advanced Institute of Science and Technology (KAIST) for helpful discussions. Financial support from the Korean Science & Engineering Foundation (R01-2000-00050) and the Korea Research Foundation (2001-041-D00119) is gratefully acknowledged.

Keywords

18-Electron dithiolate
Cyclic voltammetry
Dithiolatocobalt
Redox process

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10.1016/j.jorganchem.2003.09.019

Cite this

Kim, B. Y., Lee, C., Chung, S. W., Lee, Y. J., Pak, J. Y., Ko, J., & Kang, S. O. (2003). Electrochemical behavior of the Cp*(dithiolato)Co(III) complex [(η₅-Cp*)Co(1,2-S₂C₂ B₁₀H₁₀-S,S′)] and its derivatives: The effect of the ligand on half-sandwich cobalt(III) complexes. Journal of Organometallic Chemistry, 688(1-2), 236-245. https://doi.org/10.1016/j.jorganchem.2003.09.019

@article{bbf15628b6154516976b602652298747,

title = "Electrochemical behavior of the Cp*(dithiolato)Co(III) complex [(η5-Cp*)Co(1,2-S2C2 B10H10-S,S′)] and its derivatives: The effect of the ligand on half-sandwich cobalt(III) complexes",

abstract = "Reaction of the 16-electron dithiolatocobalt, [(η5- Cp*)Co(CabS,S′)] (1) (CabS,S′=1, 2-S2C2B10H10-S,S′), with a ligand L (L=CNtBu, PMe3, PEt3, PHPh2) affords the 18-electron complexes [(η5- Cp*)Co(CabS,S′)(L)] (2) in high yield. The structures of 2 in solution were probed by NMR spectroscopy, and the solid-state structure of the diphenylphosphine derivative was established by single-crystal X-ray diffraction. Cyclic voltammetry of 1 shows that the complex undergoes a quasi-reversible one-electron oxidation and reversible reduction. The voltammetry of the corresponding 18-electron complex 2 was investigated rather extensively in terms of coordination and redox chemistry, in which the influence of the enhanced steric interaction between the bulky Cp* and incoming ligand could be observed. Cyclic voltammograms of alkylidiene or acetylene adducts of dithiolatocobalt complex 1, [(η5-Cp*)Co{η 3-(S,S′, C′)-SC2B10 H10S(C′R2)}] [C′R2=CHSiMe 3 (3a), HC=CPh (3b), (COOMe)C=C(COOMe) (3c)], are also included.",

keywords = "18-Electron dithiolate, Cyclic voltammetry, Dithiolatocobalt, Redox process",

author = "Kim, {Bo Young} and Chongmok Lee and Chung, {Seung Won} and Lee, {Young Joo} and Pak, {Jae Youn} and Jaejung Ko and Kang, {Sang Ook}",

note = "Funding Information: We thank Prof. Sukbok Chang at the Korean Advanced Institute of Science and Technology (KAIST) for helpful discussions. Financial support from the Korean Science & Engineering Foundation (R01-2000-00050) and the Korea Research Foundation (2001-041-D00119) is gratefully acknowledged.",

year = "2003",

month = dec,

day = "15",

doi = "10.1016/j.jorganchem.2003.09.019",

language = "English",

volume = "688",

pages = "236--245",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

}

Kim, BY, Lee, C, Chung, SW, Lee, YJ, Pak, JY, Ko, J & Kang, SO 2003, 'Electrochemical behavior of the Cp*(dithiolato)Co(III) complex [(η₅-Cp*)Co(1,2-S₂C₂ B₁₀H₁₀-S,S′)] and its derivatives: The effect of the ligand on half-sandwich cobalt(III) complexes', Journal of Organometallic Chemistry, vol. 688, no. 1-2, pp. 236-245. https://doi.org/10.1016/j.jorganchem.2003.09.019

Electrochemical behavior of the Cp*(dithiolato)Co(III) complex [(η₅-Cp*)Co(1,2-S₂C₂ B₁₀H₁₀-S,S′)] and its derivatives: The effect of the ligand on half-sandwich cobalt(III) complexes. / Kim, Bo Young; Lee, Chongmok; Chung, Seung Won et al.
In: Journal of Organometallic Chemistry, Vol. 688, No. 1-2, 15.12.2003, p. 236-245.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Electrochemical behavior of the Cp*(dithiolato)Co(III) complex [(η5-Cp*)Co(1,2-S2C2 B10H10-S,S′)] and its derivatives

T2 - The effect of the ligand on half-sandwich cobalt(III) complexes

AU - Kim, Bo Young

AU - Lee, Chongmok

AU - Chung, Seung Won

AU - Lee, Young Joo

AU - Pak, Jae Youn

AU - Ko, Jaejung

AU - Kang, Sang Ook

N1 - Funding Information: We thank Prof. Sukbok Chang at the Korean Advanced Institute of Science and Technology (KAIST) for helpful discussions. Financial support from the Korean Science & Engineering Foundation (R01-2000-00050) and the Korea Research Foundation (2001-041-D00119) is gratefully acknowledged.

PY - 2003/12/15

Y1 - 2003/12/15

N2 - Reaction of the 16-electron dithiolatocobalt, [(η5- Cp*)Co(CabS,S′)] (1) (CabS,S′=1, 2-S2C2B10H10-S,S′), with a ligand L (L=CNtBu, PMe3, PEt3, PHPh2) affords the 18-electron complexes [(η5- Cp*)Co(CabS,S′)(L)] (2) in high yield. The structures of 2 in solution were probed by NMR spectroscopy, and the solid-state structure of the diphenylphosphine derivative was established by single-crystal X-ray diffraction. Cyclic voltammetry of 1 shows that the complex undergoes a quasi-reversible one-electron oxidation and reversible reduction. The voltammetry of the corresponding 18-electron complex 2 was investigated rather extensively in terms of coordination and redox chemistry, in which the influence of the enhanced steric interaction between the bulky Cp* and incoming ligand could be observed. Cyclic voltammograms of alkylidiene or acetylene adducts of dithiolatocobalt complex 1, [(η5-Cp*)Co{η 3-(S,S′, C′)-SC2B10 H10S(C′R2)}] [C′R2=CHSiMe 3 (3a), HC=CPh (3b), (COOMe)C=C(COOMe) (3c)], are also included.

AB - Reaction of the 16-electron dithiolatocobalt, [(η5- Cp*)Co(CabS,S′)] (1) (CabS,S′=1, 2-S2C2B10H10-S,S′), with a ligand L (L=CNtBu, PMe3, PEt3, PHPh2) affords the 18-electron complexes [(η5- Cp*)Co(CabS,S′)(L)] (2) in high yield. The structures of 2 in solution were probed by NMR spectroscopy, and the solid-state structure of the diphenylphosphine derivative was established by single-crystal X-ray diffraction. Cyclic voltammetry of 1 shows that the complex undergoes a quasi-reversible one-electron oxidation and reversible reduction. The voltammetry of the corresponding 18-electron complex 2 was investigated rather extensively in terms of coordination and redox chemistry, in which the influence of the enhanced steric interaction between the bulky Cp* and incoming ligand could be observed. Cyclic voltammograms of alkylidiene or acetylene adducts of dithiolatocobalt complex 1, [(η5-Cp*)Co{η 3-(S,S′, C′)-SC2B10 H10S(C′R2)}] [C′R2=CHSiMe 3 (3a), HC=CPh (3b), (COOMe)C=C(COOMe) (3c)], are also included.

KW - 18-Electron dithiolate

KW - Cyclic voltammetry

KW - Dithiolatocobalt

KW - Redox process

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U2 - 10.1016/j.jorganchem.2003.09.019

DO - 10.1016/j.jorganchem.2003.09.019

M3 - Article

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SN - 0022-328X

VL - 688

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EP - 245

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

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